O-alkyl-o-aryl-thiolphosphoric acid esters

ABSTRACT

O-ALKYL-O-ARYL-THIOLPHOSPHORIC ACID ESTERS, OF THE FORMULA   (R-O-P(=O)(-O-R&#39;&#39;)-S-CH2-CH2-),(CL)N-BENZENE   IN WHICH R IS LOWER ALKYL OF 1-4 CARBON ATOMS: R&#39;&#39; IS PHENYL, CHLORO-SUBSTITUTED PHENYL, ALKYLMERCAPTOPHENYL HAVING 1-4 CARBON ATOMS IN THE ALKYL MERCAPTO MOIEY, (ALKYL)-(ALKYLMERCAPTO)-PHENYL HAVING 1-4 CARBON ATOMS IN THE ALKYL MOIETY AND 1-4 CARBON ATOMS IN THE ALKYLMERCAPTO MOIETY, ALKOXYPHENYL HAVING 1-4 CARBON ATOMS IN THE ALKOXY MOIETY, (ALKYL)-(CHLORO)-PHENYL HAVING 1-4 CARBON ATOMS IN THE ALKYL MOIETY, OR NAPHTHYL; AND N IS A WHOLE NUMBER FROM 0 TO 2, WHICH POSSES ARTHROPODICIDAL, ESPECIALLY ACARICIDAL AND INSECTICIDAL, PROPERTIES AND WHICH MAY BE PRODUCED BY CONVENTIONAL METHODS.

United States Patent thee 3,641,221 Patented Feb. 8, 1972 3,641,221O-ALKYL-O-ARYL-THIOLPHOSPHORIC ACIID ESTERS Gerhard Schrader,Wuppertal-Cronenberg, Ingeborg Hammann, Cologne, and Wilhelm Stendel,Wuppertal- Vohwinkel, Germany, assignors to Farbenfabriken BayerAktiengesellschaft, Leverkusen, Germany N Drawing. Filed Apr. 9, 1969,Ser. No. 814,809 Claims priority, application Germany, May 9, 1968, P 1768 399.7 Int. Cl. Atlln 9/36; (307E 9/16, 9/18 US. Cl. 260-949 10 ClaimsABSTRACT OF THE DISCLOSURE O-alkyl-O-aryl-thiolphosphoric acid esters,of the formula The present invention relates to and has for its objectsthe provision for particular new 0 alkyl O arylthiolphosphoric acidesters, i.e. O-alkylO-[phenyl, chloro-substituted phenyl,alkylmercapto-phenyl, (alkyD-(alkyl-mercapto)-phenyl, alkoxy-phenyl,(alkyl)-(chloro)- phenyl, and naphthyH-S-[B-(phenyl andchloro-substituted phenyl)-ethyl]-thiolphosphoric acid esters, whichpossess arthropodicidal, especially insecticidal and acaricidal,properties, active compositions in the form of mixtures of suchcompounds with solid and liquid dispersible carrier vehicles, andmethods for producing such compounds and for using such compounds in anew Way especially for combating pests, e.g. arthropods, with other andfurther objects becoming apparent from a study of the withinspecification and accompanying examples.

Optionally chlorinated S-benzyl esters of 0,0-dial kylthiolphosphoricacids are known from German Patents 949,231 and 1,018,053, and US.Patent 3,156,718. According to the particulars given in said patents,these products, e.g. 0,0-diethyl-S-benzyl-thiolphosphoric acid ester(A), possess good insecticidal and acaricidal effectiveness with, at thesame time, low toxicity to warm-blooded animals; they are thereforeusable as pesticides in plant protection and in the hygiene field.

Furthermore, German published patent 1,252,961 describes fungicidalmixtures for use in agriculture which contain, as active component,symmetrical 0,0-dialkyl-S- (w-phenyl-alkyl) -thiolphosphoric acid esterswith 2 to 10 carbon atoms in the S-alkyl radical, e.g. 0,0-diethyl-S-(p-phenyl-ethyl)-thiolphosphoric acid ester (B).

It has now been found, in accordance with the present invention, thatthe particular new O-alkyl-O-aryl-thiolphosphoric acid esters of theformula P-S-CHz-CHz- R O (01):. (I) in which R is lower alkyl of 1-4carbon atoms;

R is phenyl, chloro-substituted phenyl, alkylmercaptophenyl having 1-4carbon atoms in the alkyl mercapto moiety,(alkyl)-(alkylmercapto)-phenyl having 1-4 carbon atoms in the alkylmoiety and 1-4 carbon atoms in the alkylmercapto moiety, alkoxy-phenylhaving 1-4 carbon atoms in the alkoxy moiety, (alkyl)-(chloro)- phenylhaving 1-4 carbon atoms in the alkyl moiety, or naphthyl; and

n is a whole number from 0 to 2;

exhibit strong arthropodicial, especially insecticidal and acaricidal,properties.

It has been furthermore found, in accordance with the present invention,that a process may be provided for the production of the compounds ofFormula I above, which comprises hydrolyzing anO-alkyl-O-aryl-thionophosphoric acid ester halide of the general formulain which R and R are the same as defined above, and Hal is a halogenatom such as chloro, bromo, fluoro or iodo, especially chloro, and thenreacting the hydrolysis product thereby formed, expediently withoutprevious isolation, with a B-phenyl-ethyl halide of the general formulain which Hal and n are the same as defined above.

Advantageously, the particular new compounds of Formula I above aredistinguished by outstanding insecticidal and acaricidal properties;they possess both a very good activity against eating and suckinginsects and an excellent effectiveness against spider mites and ticks;furthermore, some of them possess a good fungitoxic side-effect.Surprisingly, the instant compounds, compared to the previously knownactive compounds of analogous constitution and the same direction ofactivity, such as compounds (A) and (B) mentioned above, possesssubstantially better eifectiveness, with considerably lower toxicity towarmblooded animals and concomitantly low phytotoxicity. The newcompounds of the present invention therefore represent a genuineenrichment of the art.

The course of the production process according to the present inventionis illustrated by the following reaction scheme:

( (III) In the above equations, R, R, Hal and n are the same as definedabove, and M is a monovalent metal equivalent, e.g. alkali metal such aspotassium, or the ammonium group.

Advantageously, in accordance with the present invention, in the variousformulae herein:

R represents straight and branched chain lower alkyl of 1-4 carbon atomssuch as methyl, ethyl, nand iso-propyl, n-, iso-, sec. and tert.-butyl,and the like, especially C or C alkyl, and more especially ethyl;

R' represents:

Phenyl;

chloro-substituted phenyl such as mono-, diand trichloro-phenyl,including 2-, 3- and 4- mono-; 2,3-, 2,4- 2,5-, 2,6- 3,4- and 3,5- di-;and 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,45- tri- -chloro-phenylespecially chlorophenyl of 1-3 chloro substituents;

Alkylmercapto-phenyl having l-4 carbon atoms in the alkylmercapto moietysuch as methyl to tert.-butyl inclusive as defined above, and the like,-mercapto-phenyl, including 2-, 3- and 4-C or C or Calkylmercaptophenyl, especially methylmercapto-phenyl;

(Alkyl)-(alkylmercapto)-phenyl having 1-4 carbon atoms in the alkylmoiety and 1-4 carbon atoms in the alkylmercapto moiety such as (methylto tert.-butyl inclusive as defined above, and the like)-(methyl totert.- butyl inclusive as defined above, and the like, -mercapto)-phenyl, including 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-, i.e. mixed, (Cor C or C alkyl, especially methyl)- (C or C or C alkylmercapto,especially methylmercapto)-phenyl;

Alkoxy-phenyl having l-4 carbon atoms in the alkoxy moiety such asmethoxy, ethoxy, nand isopropoxy, n-, iso-, sec.- and tert.-butoxy, andthe like, -phenyl, including 2-, 3- and 4- C or C or C alkoxy-phenyl,especially methoxy-phenyl;

(Alkyl)-(chloro)-phenyl having 1-4 carbon atoms in the alkyl moiety suchas (methyl to tert.-butyl inclusive as defined above, and thelike)-(chloro)-phenyl, including 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-,i.e. mixed, (C, or C or C alkyl, especially methyl)-(chloro)-phenyl; ornaphthyl;

n represents a whole number from 0 to 2, ie, 0, l or 2, especially 0 or1,

Such that, when n=1, (Cl) is 2-, 3- or 4- chloro, and, when n=2, (Cl) is2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichloro, i.e. with respect to thecorresponding phenyl nucleus.

Preferably, R is (3 alkyl, especially ethyl; R is phenyl; or mono totrichloro-substituted phenyl; or C alkylmercapto-phenyl, especiallymethylmercapto-phenyl; or (C alkyl)-(C alkylmercapto)-phenyl, especially(methyl)-(methylmercapto)-phenyl; or C alkoxyphenyl; or (Calkyl)-(chloro)-phenyl; or naphthyl; and n is 0-1.

Some of the O-alkyl-O-aryl-thionophosphoric acid ester halides ofFormula II above required as starting materials for the productionprocess according to the present invention are described in theliterature. These starting compounds can be prepared, even on anindustrial scale, according to known methods by reaction of theappropriate O-alkyl-thionophosphoric monoester dihalides with suitablephenols in the presence of acid-binding agents. The reaction takes placepreferably in aqueous-alkaline solution at room temperature or slightlyelevated temperature.

Suitable starting materials include the following 0-alkyl-O-aryl-thionophosphoric acid ester halides, for example:

O-ethyl-O-phenyl-, O-ethyl-O-(2-ch1oro-phenyl)-,

4 O-ethyl-O- (3 -chloro-phenyl O-ethyl-O- (4-chloro-phenyl)O-ethyl-.O-(2,4- and. 2,5 -dichloro -phenyl)-., O-ethyl-O- 2,4,5 and2,4,6-trichloro-pheny1)-, O-ethyl-O- 2-chloro-4-methyl-phenyl)O-ethyl-O- 3-chloro-4-methyl-pheny1) O-ethyl-O-3-methyl-4-chloro-pheny1) O-ethyl-O- (2-methyl-4-chloro-phenyl O-ethyhO-2-chloro-4-tert.-butyl-phenyl) O-ethyl-O- (4-methoxy-phenyl) O-ethyl-O-3 -methoxyphenyl O-ethyl-O- (-Z-methoxy-phenyl) O-ethyl-O-(4-methylmercapto-phenyl) O-ethy1-O-( 3-methyl-4-methylmercaptophenyl)O-ethyl-O- Z-methyl-4-methylmercapto-phenyl) andO-ethyl-O-naphthylthionophosphoric acid ester chlorides and bromides andthe corresponding O-methyl, -n-propyl and -isopropyl compounds.

The 2-phenyl-ethyl halides of Formula III above which may be used assecond reaction component are also known from the literature. 7

As examples of such starting Z-phenyI-ethyl halides which may be reactedaccording to the instant process, there are mentioned in particular:

fi-phenyl-ethyl chloride,

fl-(2-chloro-phenyl) -ethyl chloride,

[5- 3-chloro-phenyl-) -ethyl chloride,

fi-(4-chloro-phenyl-)-ethyl chloride, and

,B-(2,4-, 3,4- and 2,5-dichloro-phenyl)'-ethyl chlorides and thecorresponding bromides.

Both the first and the second step of the reactionaccording to theprocess are carried out preferably in the pres ence of a solvent (theterm solvent as used herein including mere diluents). While thehydrolysis reaction preferably proceeds in aqueous or aqueous-alcoholicsolution, the reaction with the ,B-phenyl-ethyl halides can be. carriedout in practically all organic solvents or mixtures thereof. Theseinclude aliphatic or aromatic (possibly chlorinated) hydrocarbons suchas benzine, methylene chloride, benzene, toluene, chlorobenzene, xylene;ethers, for example diethyl or di-n-butyl ether, dioxan ortetrahydrofuran; and low-boiling point aliphatic alcohols,'ketones andnitriles, for example methanol, ethanol, isopropanol, butanol, acetone,methylethyl ketone methylisopropyl ketone, methylisobutyl ketone-and.acetonitrile and propionitrile; and the like.

=Hydrolyzing agents suitable for the instant process are chieflyalkalie's, preferably aqueous or aqueous-alcoholic solutions of sodiumhydroxide or of potassium hydroxide.

The process can be carried out within a fairly wide temperature range.In general, the work is carried out at substantially between about 20l00C. (or the boiling point of the mixture), preferably at between about20- C.

As can be seen from the foregoing reaction scheme, about 2 mols ofalkali and about 1 mol of B-phenyl-ethyl halide are required per mole ofO-alkyl-O-aryl-thiophosphoric acid ester halide. It has proved expedientto add the solution of alkali to the aqueous or aqueous-alcoholicsolution of the ester chloride, adding the 3-phenyl-ethy1 halideundiluted (after completion of the hydrolysis and possibly withoutisolation of the intermediate product formed) to the reaction mixturewith stirring, and then continuing heating to the temperatures statedfor a longer period (1 to 3 hours) in order to complete the reaction.With this method of working, the instant products are obtained withoutstanding yields and in excellent purity.

The working up of the reaction mixture takes place in theu'sual manner,for example by taking it up in a solvent not miscible with water orwater/alcohol, separating the phases, washing and drying of the organiclayer, evaporation of the solvent and, if desired, fractionaldistillation of the residue.

phenyl, alkylmercapto-phenyl having 1-4 carbon atoms in theal'kylmercapto moiety, (al kyl)-( alkylmercapto)- phenyl having 14carbon atoms in the alkyl moiety and 1-4 carbon atoms in thealkylmercapto moiety, alkoxyphenyl having '1-4 carbon atoms in thealkoxy moiety, (alky1)-(chloro)-penyl having 1-4 carbon atoms in thealkyl moiety, and naphthyl, and n is a whole number from -2.

2. Compound according to claim 1 wherein R is C alkyl, R is selectedfrom the group consisting of phenyl, mono to trichloro-substitutedphenyl, C alkylmercaptophenyl, (C alky1)-(C alkylmercapto)-phenyl, Calkoxy-phenyl, (C alkyl)-chloro)-phenyl, and naphthyl, and n is 0-1.

3. Compound according to claim 1 wherein such compound isO-ethyl-O-phenyl-S-(fl-phenyl-ethyl)-thiolphosphoric acid ester of theformula 4. Compound according to claim 1 wherein such compound isO-ethyl-O- (4-chloro-phenyl -S- (fl-phenyl-ethyl thiolphosphoric acidester of the formula 6. Compound according to claim 1 wherein suchcompound is O ethyl'O-(3-methoxy-phenyD-S-(ii-phenylethyl)-thiolphosphoric acid ester ofthe formula CHQO 7. Compound according to claim 1 wherein such compoundis O-ethyl-O-(3-methyl-4-methylmercapto-phenyl)- 28 S-(fi-phenyl ethyl)thiolphosphoric acid ester of the formula 8. Compound according to claim1 wherein such compound is O ethyl O-(2-methyl-4-chloro-phenyl)-S-(B-phenyl-ethyl)-thiolphosphoric acid ester of the formula 9. Compoundaccording to claim 1 wherein such compound is O ethylO-(fl-naphthyl)-S-(fi'-phenyl-ethyl)- thiolphosphoric acid ester of theformula References Cited UNITED STATES PATENTS 5/ 1960 Lorenz et al260949 CHaS- CHARLES B. PARKER, Primary Examiner R. L. RAYMOND,Assistant Examiner U.S. Cl. X,R.

of 200 ml. of water and 200 ml. ethanol. To this solution there areadded at 20 C., with stirring, 60 g. potassium hydroxide in 120 ml. ofwater. The temperature of the mixture rises to 70 C. In order tocomplete the hydrolysi-s, the reaction mixture is then boiled for 4hours and 110 g. B-(4-chloro-phenyl)-ethyl bromide are then added to itat 80 C., with further stirring. The mixture is heated at thetemperature stated for a further 2 hours and then cooled. Finally, themixture is taken up in 400 ml. methylene chloride, the methylenechloride solution is washed with water until there is a neutralreaction, the organic phase is separated and dried, the solvent isevaporated and the residue is slightly distilled at 100 C. at a pressureof 0.01 mm. Hg. I

There are obtained in this manner 95 g. (41% of the theory) ofO-ethyl-O- (4-chloro-phenyl) -S [B- (4-chlorophenyl)-ethyl]-thiol-phosphoric acid ester in the form of a non-distillable oil with arefractive index of n =1.5690.

Calculated for C H C1 O PS (molecular weight 391) (percent): P, 7.9; S,8.2; C1, 18.2. Found (percent): P, 8.2; S, 7.8; Cl, 17.9.

EXAMPLE 14 48 g. potassium hydroxide dissolved in 100 ml. of water areadded at 20 C., with stirring, to a soltuion of 110 g. (0.4 mol)O-ethyl-O-(3-chloro-phenyl)-thionophosphoric acid ester chloride in 200ml. of water and 200 ml. of ethanol, the temperature of the mixturerising to 70 C. After completion of the addition, the mixture is boiledfor 4 hours. 88 g. fl-(4-chloro-phenyl)-ethyl bromide are subsequentlyadded to the reaction mixture at 80 C., and the mixture is heated atthis temperature for 2 hours and, finally, it is cooled. After cooling,the mixture is taken up in methylene chloride.

The methylene chloride solution is washed until it gives a neutralreaction, dried, and the solvent is evaporated. The residue is slightlydistilled at 90 C./0.01 mm. Hg. The O-ethyl-O-(3 chloro-phenyD-S-[B-(4chloro-phenyl)- ethyl]-thiolphosphoric acid ester is obtained as awaterinsoluble oil which can be distilled in small amounts at 140 C.under a pressure of 0.01 mm. Hg and possesses the refractive index n=1.5708.

The yield is 80 g. (51% of the theory).

Calculated for C H Cl O PS (molecular weight 391) (percent): P, 7.9; S,8.2; Cl, 18.2. Found (percent): P, 7.9; S, 8.2; CI, 17.6.

EXAMPLE 15 CzHsO O In an analogous manner to that described in Example14 there are obtained, by hydrolysis ofO-ethyl-O-(Z-chlorophenyl)-thionophosphoric acid ester chloride andsubsequent reaction with 18-(4-chloro-phenyl)-ethyl bromide, 75 g. (48%of the theory) of O-ethyl-O-(2-chloro-phenyl)- S-[fl-(4chloropheny1)-ethyl] -thiolphosphoric acid ester as non-distillable,water-insoluble oil with the refractive index n =1.5667, but which canbe slightly distilled at 80 C./0.01 mm. Hg.

Calculated for C16H1qCl203PS (molecular weight 391) (percent): P, 7.9;S, 8.2; CI, 18.2. Found (percent): P, 8.0; S, 7.6; CI, 18.1.

26 EXAMPLE 16 By reaction of 114 g. (0.4 mol)O-ethyl-O-(4-methylmercapto-phenyl)-thionophosphoric acid ester chloridewith aqueous-alcoholic solution of potassium hydroxide at 20 to 60 C.and subsequent reaction with 88 g. )3-(4- chloro-phenyl)-ethyl bromideunder the conditions stated in Example 14, and slight distillation ofthe reaction product at C./0.0l mm. Hg, theO-ethyl-O-(4-methylmercapto-phenyl -S- [5- (4'-chloro-phenyl -ethyl]-thiolphosphoric acid ester is obtained in the form of an oil which iswater-insoluble and cannot be distilled, and has the refractive index n=1.5942.

The yield is g. (53% of the theory).

Calculated for C H ClO PS (molecular weight 402.5) (percent): P, 7.7; S,15.9; C1, 8.8. Found (percent): P, 7.6; S, 14.9; CI, 9.5.

EXAMPLE 17 Cz\H O 142 g. (0.5 mol) O-ethyl-O-(4methylmercapto-phenyl)-thionophosphoric acid ester chloride arehydrolyzed at 20 to 70 C. in the manner described in the precedingExamples with 60 g. potassium hydroxide dissolved in 120 ml. of waterand subsequently reacted with 93 g. B-phen' yl-ethyl bromide.

After slight distillation of the reaction product at 70 C. under apressure of 0.01 mm. Hg, g. (57% of the theory) of theO-ethyl0-(4-methylmercapto-phenyl)-S- (B-phenyl-ethyl)-thiolphosphoricacid ester are obtained as a water-insoluble oil which can be distilledin small amounts, the distillate of which boils at 134 C./0.01 mm. Hgand possesses the refractive index n =1.5890.

Calculated for C H O PS (molecular weight 368) (percent): P, 8.4; S,17.4. Found (percent): P, 8.3; S, 17.4.

It will be realized that all of the foregoing compounds contemplated bythe present invention possess the desired selective pesticidal,especially arthropodicidal, i.e. insecticidal or acaricidal, propertiesfor combating insects and acarids, and that such compounds have not onlya very slight toxicity toward warm-blooded creatures, but also aconcomitantly low phytotoxicity.

As may be used herein, the terms arthropod, arthropodicidal andarthropodicide contemplate specifically both insects and acarids. Thus,the insects and acarids may be considered herein collectively asarthropods to be combated in accordance with the invention, andaccordingly the insecticidal and/or acaricidal activity may be termedarthropodicidal activity, and the concomitant combative or effectiveamount used will be an arthropodicidally effective amount which ineffect means an insecticidally or acaricidally effective amount of theactive compound for the desired purposes.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. O-alkyl-O aryl thiolphosphoric acid ester of the formula in which Ris alkyl of l-4 carbon atoms, R is selected from the group consisting ofphenyl, chloro-substituted 23 Yield: 56% of the theory ofO-ethyl-O-(2,4,5-trichlorophenyl)-S-(fi-phenyl-ethyl)-thiolphosphoricacid ester.

Calculated for C H Cl O PS (molecular weight 425.5) (percent): P, 7.3;S, 7.5. Found (percent): P, 7.5; S, 7.7.

( CH3 (III) Yield: 72% of the theory ofO-ethyl-O-(2-methoxy-phenyl)-thionophosphoric acid ester chloride, B.P.95 C./ 0.01 mm. Hg.

Calculated for C H ClO PS (molecular weight 266.5) (percent): P, 11.6;S, 12.0; CI, 13.3. Found (percent): P, 11.6; S, 12.0; C1, 13.5.

Yield: 60% of the theory ofO-ethyl-O-(Z-methoxyphenyl)-S-(/3-phenyl-ethyl) -thiolphosphoric acidester.

Calculated for C H O PS (molecular weight 352) (percent): P, 8.8; S,9.1. Found (percent): P, 8.4; S, 9.6.

( 0) CzH5O\ S ll P-Cl l) CzHsO O Yield: 53% of the theory ofO-ethyl-O-(3-methoxy-phenyl)-S-(}3-phenyl-ethyl)-thiolphosphoric acidester.

Calculated for C17H21O4PS (molecular Weight 352) (percent): P, 8.8; S,9.1. Found (percent): P, 8.8; S, 9.2.

EXAMPLE CzH 0 o 95 g. 0.4 mol) 0-ethyl-O-phenyl-thionophosphoric acidester chloride are dissolved in 300 ml. ethanol. 48 g. potassiumhydroxide in 100 ml. of water are added to this solution at 20 C., withstirring. The temperature of the mixture rises to 70 C. The mixture isheated at this temperature for a further hour and 88 g.fi-(4-chloro-phenyl)- ethyl bromide are then added to it, with furtherstirring. The reaction mixture is subsequently heated to 70 to 80 C. fora further 2 hours. The mixture is cooled to room temperature and takenup with 300 ml. methylene chloride. The methylene chloride solution isseparated, washd with water, dried over sodium sulfate and, finally, thesolvent is distilled off. When fractional distillation of the residue iseifected, 48 g. (31% of the theory) of O-ethyl- O phenyl S 3 (4chloro-phenyl)ethylJ-thiol-phosphoric acid ester are obtained in theform of a colorless, water-insoluble oil which boils at 140 C. at apressure of 0.01 mm. Hg.

24 Calculated for C H CIO PS (molecular weight 356.5) (percent): P, 8.7;S, 9.0; Cl, 9.9. Found (percent): P, 9.0; S, 9.0; Cl, 9.3.

The mediantoxicity of the compound in the rat per os is 750 mg./kg. a

1 EXAMPLE 11- 116 g. O-ethyl-O-(fi-naphthyl) thionophosphoric acid acidmonoester dichloride and B-naphthol in the manner described in Example9(a), B.P. 135 C./0.0l mm. Hg] are dissolved in a mixture of 200 ml.ethanol and 50 ml. of water, and to this solution there are added, withstirring, 50 g. potassium hydroxide dissolved in 50 ml. of water. Thetemperature of the mixture rises to 70 C. 74 g. ,B-phenyl-ethyl bromideare then added with further stirring, the temperature being kept at 70to 80 C. for a further 2 hours. The reaction mixture is then cooled and400 ml. benzene are added. The benzene solution obtained is separated,washed with water, dried over sodium sulfate and, finally, the solventis distilled off. The residue is heated in a distillation apparatus at70 C. for 20 minutes at a pressure of 0.01 mm. Hg.

88 g. (59% of the theory) of O-ethyl-O-(B-naphthyD- S- (B'-phenyl-ethyl)-thiolphosphoric acid ester are obtained as colorless, water-insolubleoil.

Calculated for C H O PS (molecular weight 372) (percent): P, 8.3; S,8.6. Found (percent): P, 8.0; S, 8.5.

EXAMPLE 12 60 g. potassium hydroxide dissolved in 180 ml. of water areadded, with stirring, to a solution of 163 g. O-ethyl- O-(2-chloro-4-tert.-butyl-phenyl)-thionophosphoric acid ester chloride[prepared by reaction of O-ethyl-thionophosphoric acid monoesterdichloride with 2-chloro-4- tert.-butyl-phenol in the manner describedin Example 9(a)] in 150 ml. ethanol. The temperature of the reactionmixture rises to 70 C. The mixture is heated at C. for a further hourand 93 g. fl-phenyl-ethyl bromide are then added, with further stirring.The temperature of the mixture is kept at C. for a further 2 hours. Themixture is then allowed to cool and taken up in 400 ml. benzene. Thebenzene solution is washed with water, sepa rated, and dried over sodiumsulfate. After the benzene has been distilled off, the residue is heatedat a bath temperature of C. for 20 minutes at a pressure of 0.01 mm. Hg.

90 g. (44% of the theory) of O-ethyl-O-(2-chloro-4-tert.-butyl-phenyl)-S-(B phenyl-ethyl)-thiolphosphoric acid ester areobtained as a water-insoluble, pale yellow oil.

Calculated for C dH ClO PS (molecular weight 412.5) (percent): P, 7.5;S, 7.8; CI, 8.6. Found (percent): P, 7.4; S, 7.9; Cl, 8.9.

EXAMPLE 13 C2H5O O g. (0.5 mol) O-ethyl-O-(4-chloro-phenyl)-thiono--phosphoric acid ester chloride are dissolved in a mixture 21 EXAMPLE.

v $l S-CH zCHz CzH O (73) 38 g. potassium hydroxide dissolved in '60 g.of water are added, with cooling, to a solution of 89 g. (0.3 mol) of Oethyl-O-(3-methyl-4-methyl-mercapto-phenyl)-thionophosphoric acid esterchloride in 150 ml. ethanol and 40 ml. of water. 55 g. fi-phenethylbromide are then added dropwise to the reaction mixture at 70-80 C.Thereafter the mixture is stirred for 2 hours at 80 C., then poured intoice water, taken up with benzene and the benzene phase is dried anddistilled. 75 g. (66% of the theory) of 'O-ethyl O(3-methyl-4-metl1ylmercaptophenyl)-S-(B-phenyl-ethyl)-thiolphosphoricacid ester of boiling point 120 C./ 0.01 mm. Hg. are obtained.

Calculated for C H O PS (molecular weight 382) (percent): P, 8.1; S,16.7. Found (percent): P, 7.9; S, 17.2.

CHaS

193 g. 2-chlorophenol dissolved in 250 cc. of water and 66 g. sodiumhydroxide are added, at 20 C., to 269 g. (1.5 mols)O-ethyl-thionophosphoric acid monoester dichloride. After three hoursstirring, the reaction mixture is taken up in ether, the etherealsolution is washed until there is a neutral reaction, then dried, andthe solvent is evaporated and the residue is distilled.

The yield of O-ethyl-O-(2-chloro-phenyl)-thionophosphoric acid esterchloride is 245 g. (60% of the theory), with a boiling point of 90 C./0.01 mm. Hg.

Calculated for C H Cl O PS (molecular weight 271) (percent): P, 11.4; S,11.8; C1, 26.2. Found (percent): P, 11.5; S, 11.8; Cl, 25.9.

(b) C 2H5 0 O 48 g. potassium hydroxide in 100 g. water are added at 20to 70 C. to a solution of 108 g.0-ethyl-O-(2-chlorophenyl)-thionophosphoric acid ester chloride in 250ml. ethanol and 50 ml. water. 74 g. p-phenethyl bromide are then addedto the mixture and the latter is heated to 80 C. for 2 hours. Finally,the reaction mixture is taken up in benzene, the benzene solution iswashed until there is a neutral reaction, the solvent is evaporated andthe residue is slightly distilled.

The yield ofO-ethyl-O-(2-chloro-phenyl)-S-(;B-phenylethyD-thiolphosphoric acid esteris 60 g. (42% of the theory). I

Calculated for C' H C1O PS (molecular weight 356.5) (percent): P, 8.7;S, 9.0. Found (percent): P, 9.3; S, 9.4.

In analogous manner, the following compounds are obtained:

( t) 02H; 0 S

Yield: 63% of the theory of O-ethyl-O-(3-chloro-pheny1)-thionophosphoric acid ester chloride, B.P. 90 C./0.01 ngrmldg Yield: 24%of the theory of O-ethyl-O-(3-chloro-phenyl)-S-(fl-phenyl-ethyl)-thiolphosphoric acid ester Calculated for C H gClOPS (molecular weight 356.5) (percent): P, 8.7 S, 9.0. Found (percent):P, 9.1; S, 9.3.

(IIc) Yield: 71% of the theory of. O-ethyl-O-(2-chloro-4-methylphenyl)-thionophosphoric acid ester chloride, B.P. 110C./0.01 mm. Hg.

Calculated for C H CI O PS (molecular weight 285) (percent): P, 10.9; S,11.2; C1, 24.9. Found (percent): P, 10.9; S, 11.3; C], 25.2.

(51 Yield: 54% of the theory ofO-ethyl-O-(2-chloro-4-methylphenyl)-S-(fl-phenyl-ethyl)-thiolphosphoricacid ester.

Calculated for C H ClO PS (molecular weight 370.5) (percent): P, 8.4; S,8.6. Found (percent): P, 9.1; S, 9.0.

( 3) CQHEO S (311; (IN) Yield: 61% of the theory ofO-ethyl-O-(2-methyl-4-chlorophenyl)-thionophosphoric acid esterchloride, B.P. C./0.01 mm. Hg.

Calculated for C H CI O PS (molecular weight 285 (percent): P, 10.9; S,11.2; CI, 24.9. Found (percent): P, 10.7; S, 11.3; CI, 24.9.

Yield: 48% of the theory of O-ethyl-O-(2-methyl-4-chlorophenyl)-S-(fi-phenyl-ethyl)-thiolphosphoricacid ester. Calculated for C H ClO PS (molecular weight 370.5)(percent): P, 8.4; S, 8.6. Found (percent): P, 8.4; S, 8.8.

Calculated for C H7Cl4O2PS (molecular weight 340) (percent): P, 9.1; S,9.4. Found (percent): P, 8.6; S, 8.9.

TABLE 6Continued Concentration of active Degree of compound destructionActive compound in percent in percent (17 Cl 0. 2 100 0. 02 90 @Kt C/PS-CHz-GHr- -C1 CzHsO (164) Cl 0. 2 100 I 0. 02 100 @Kt P- s CHzCHz-Cl2 50 (122) Cl 0. 2 100 l 0. 02 100 P S H2- 0 H2- CzHsO P-S-CHr-CHr- Ol CzHsO (72) CH 0. 2 100 l o. 02 100 0 Ha S 0 P- s -omorrr@ CzHsO (94) 0. 1100 O O 0. 01 100 0. 001 so P- S O HzO H2 01 CzHrO (19 0. 2 100 CHaS-0\() 0.02 100 /PS-CHzCHz-Cl 2 50 (62) O 0 H3 0. 2 100 l 0. 02 70 P- s-CHz-CH2- 2 50 The following further examples are set forth toillustrate, without limitation, the process for producing the 5particular new compounds in accordance with the present invention.

*EXAMPLE 7 CzHgO O 95 g. (0.4 mol) '0-ethyLO-phenyl-thionophosphoricacid ester chloride are dissolved in 200 ml. ethanol and ml. water, and48 g. potassium hydroxide in 100 ml. water are added to this solution.The mixture is then stirred for 1 hour until there is a neutralreaction, the solvent is evaporated and the residue is taken up in 200ml. acetonitrile. 74 g. fl-phenethyl bromide are added to this solutionand it is then heated at 70 to 80 C. for 2 hours. After that, thereaction mixture is poured into water, taken up with benzene, thebenzene phase is separated, washed and dried, the solvent is evaporatedand the residue is slightly distilled.

The yield of O-ethyl-O-phenyl-S-(fi-phenyl-ethyl)-thi01- phosphoric acidester is 96 g. (75% of the theory).

Calculated for C H O PS (molecular weight 322) (percent): S, 10.0; P,9.7. Found (percent): '8, 10.4; P, 10.3.

In analogous manner, the following compounds can be prepared:

Yield: of the theory of O-ethyl-O-(4-chloro-phenyl)-S-(B-phenyl-ethyl)-thiolphosphoric acid ester Calculated for C H ClO PS(molecular weight 357) (percent): S, 9.0; P, 8.7; CI, 10.0. Found(percent) S, 8.9; P, 8.9; Cl, 10.6.

TABLE -Continued [Mosquito larvae test] Concentration of active compoundin Degree of the solution destruction Active compound in ppm. in percentI I r somcm Cl 32 50 1 /r -scHl-om CzHsO 5 CH 0 1 100 2) I a 0 1 90Ps-crnom- CzHsO 3 01 0.1 100 a) I l? C2 sO PS-CH2CH2@ CaHsO EXAMPLE 6Petri dish remains uncovered until the solvent has completelyevaporated. The amount of active compound per test square metre offilter paper varies with the concentration Test creatures: Sitophilusgranarius Solvent: Acetone 2 parts by weight of the particular activecompound of the solution of active compound used. About 25 testcreatures are then placed in the 'Petri dish and the dish is coveredwith a glass lid.

The condition of the test creatures is observed after 1 and after 3 daysfrom the commencement of the experiments. The knockdown eifect isdetermined as a percentage.

The particular active compounds tested, their concentrations, the testcreatures and the results obtained can be seen from the following Table6:

TABLE 6 [LDruo test] Concentration of active Degree 01' compounddestruction Active compound in percent in percent ll /P-S--CH2CH2 CzHsII I P S C H2C H2- 01 (3n) Cl 0. 2 100 I (fi 0. 02

| P-S-OH CH- 01 P Q TABLE 4-Corrtinued Active compound CrHaO Degree ofConcentration destruction of active comin percent pound in after 3percent days EXAMPLE 5 Mosquito larvae test Test creatures: Aedesaegypti (5th larval stage) Solvent: 99 parts by weight acetoneEmulsifier: 1 part by weight benzylhydroxydiphenyl poly glycol ether Toproduce a suitable preparation of the particular active compound, 2parts by weight of such active compound are dissolved in 1000 parts byvolume of the solvent containing the amount of emulsifier stated above.The

be seen from the following Table 5:

TABLE 5 [Mosquito larvae test] Concentration active compound in Degreeof the solution destruction Active compound in percent in ppm.

(182) 1, mo 01- 0\fi0 0.1, M e0 z sO a" 0.: as

m i -s-cHicHr-c1 IHBO I (17,) 31

l S-CH2CH2-c1 CzHuO zHaO 19 I 1 1'00 on3s-o 0.1 A

TABLE 3 [Tick test] Concentration of active Inhibition compound oi thedepositing solution of eggs Active compound Parasite in percent inpercent (1 Boophilns 1. 0 100 ll microplns 0. 1 100 OPS CHr-CHsensitive. 0. 01 100 I 0. 001 100 021150 0. 0001 100 0. 00001 0 (14) OBoaphilns 1. 0 100 ll microplm 0. 1 100 OPS CHrCH resistant. 0. 01 100(L; 0. 001 50 21150 0.0001 0 (2;) O Boophzlns 1. 0 100 II mic'mplm 0. 1100 C1 OPS -CH2-C H sensitive. 0. 01 100 a 0. 001 100 I CzH O 0. 0001100 0. 00001 50 (24) 0 Boophilns 1. 0 100 iI microplns 0. 1 100 CI -OS-CHz-CH resistant. 01 100 I 0. 001 50 C2H5O 0. 0001 0 (3s) ClBoophilns 1. 0 100 0 microplns 0. 1 100 ll sensitive. 0. 01 100 C1OPS-CHz-CH 0. 001 100 I 0. 0001 100 02151 0 0. 00001 50 (3 ClBoophilns 1. 0 100 -O' -micropl'ns 0.1 100 ll resistant. 0. 01 100 C1OI|SCHz-CH 0.001 0 EXAMPLE 4 Cabbage leaves (Brasslca oleracea) aresprayed with Plutella test Solvent: 3 parts by weight acetoneEmulsifier: 1 part by weight alkylaryl polyglycol ether the given activecompound preparation until dew moist and are then infested withcaterpillars of the diamondback moth (Plutella maculipennis).

After the specified period of time, the degree of destruction isdetremined as a percentage: 100% means that all the caterpillars arekilled whereas 0% means that none of the caterpillars are killed.

The particular active compounds tested, their concentrations, theevaluation time and the results obtained can be seen from the followingTable 4:

TABLE 4 [Plutella test] Degree of Concentration destruction of activecomin percent pound in after 3 Active compound percent days (B) 0 0. 1100 II 0. 01 0 (CzH)2PC-CH2CH2 no n) (152) ll 0. 1 100 P-S OHz-Clh- 00.01 100 V 001 2 50 17, Q 0.1 O O 0. 01 100 H /P-SCH2CH2 C1 C1 C2H5O O O rl|- 0. 1 100 (162) P-SCHz-CH2 Cl 0.01 100 0. 001 80 12 Adult, g'orged,female ticks of the species B ophilus miqqrl t t enat ef r a,.2e itaaarssriqtiyely.) ar limthe spider mites are killed whereas means thatnone" of the spider mites are killed.

The particular active compounds tested, their concentrations, theevaluation time and the-results obtained can be seen from the followingTable 2:

mersed for one minute in the given active compound preparations. Afterimmersion of, in each case, female HspecimenSJOfHthe.different types$'1i'i 's, ini'e. latter. are

transferred to Petri dishes, the bottom of each of which is TABLE 2[Tetranychus test] Coneentra- Degree of tlon of active destructioncompound in in percent Active compound percent after 48 hours (A) fl)0.1 o

amour-GHQ (known) P-S-CHz-CH -Q 021150 \ll /PS-CH2CH CzHsO r-s-om-onr021150 r-s-omom 01 9 0.1 100 2) Q-og: 0.01 75 P-S-OHz-CHa-Q 01P-S-CHz-CHz-Q G1 I r-s-cm-cm-Q 021150 1 =-s-oHr-ot1-or CZ aO EXAMPLE 3covered with a correspondingly large disc of filter paper. Tick testAfter 10 days the eflf'ectiveness of the preparation of Solvent: 35parts by weight ethylg lycol monomethyl ether Emulsifier: 35 parts byweight nonylphenol polyglycol ether the given active compound isdetermined by ascertaining the inhibition of the depositing of eggs incomparison with untreated control ticks. The effect is expressed as apercentage, 100% meaning that no eggs are deposited, and 0% signifyingthat thetick deposited eggs in normal amount.

The particular active compounds tested, their concentrations, the testparasites and the results obtained can he seen from the following Table3:

TABLE 1Contlnued [Phaedon-larvae test] Concentra- Degree of tion ofactive destruction 1 1 compound in in percent Active compound percentafter 3 days P'SCHQ CH C 0111 0 Ps-oH1-oH1 P-s-cH1cH1 CzHsO (71) 0H1 0.1100 0. 01 100 ems-Q0 o \ll PSCH2-CH2- C2Hs (s1)- 0.1 100 o 0. 01 100P-S-CHzCHzc1 C2H5O (91) 0.1 100 O O 0. 01 100 \II 0. 001 00 P-S-OHr-CHr-01 CzHsO P-SCHCHrc1 CZHSO PSCH2-CH2- CH3 (121 G1 0.1 100 l 0. 01 95(CHa)s-CO 0 \Il /PS--CH2CH2- 021150 (131) CI 0.1 100 I 0. 01 100 P-S-CH-CHz- Cl CQHEO P-S-CHr-CHrg C2H50 EXAMPLE 2 concentrate is diluted withwater to the desired final con- Tetran chus test centratlon' y Beanplants (Phaseolus vulgarzs), which have a height Solvent: 3 Parts yWelght acetone 0 of approximately 10-30 cm., are sprayed with the prepa-Emulsifieli 1 P511rt y Weight alkylaryl Polyglycol ether 7 ration of thegiven active compound until dripping wet. T produce a i bl preparationof h particular These bean plants are heavily infested with spider mitesactive compound, 1 part by weight of such active com- (Tetmnychusfelarius) in all Stages of developmentpound is mixed with the statedamount of solvent con- After the specified period of time, theeffectiveness of taining the stated amount of emulsifier and theresulting 75 the active compound preparation is determined by countsolidand/r liquid dispersible carrier vehicles and/or with other knowncompatible active agents, especially plant protection agents, suchasother acaricides or insecticides, or fungicides, herbicides,bactericides, etc., if desired, or in the form of particular dosagepreparations for specific application made therefrom, such as solutions,emulsions, suspensions, powders, pastes, and granules which are thusready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95% by weight, andpreferably 05-90% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.0000120%, preferably 0.01-5 by weight ofthe mixture. Thus, the present invention contemplates over-allcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as (1) a dispersible inert finely divided carriersolid, and/or (2) a dispersible carrier liquid such as an inert organicsolvent and/or water preferably including a surface-active efiectiveamount of a carrier vehicle assistant, e.g. a surface-active agent, suchas an emulsifying agent and/or a dispersing agent, and an amount of theactive compound which is effective for the purpose in question and whichis generally between about 0.0000195%, and preferably 0.01-95 by weightof the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e., by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in finelydivided form, e.g. average particle diameter of from 50- 100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-l6 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of activecompound or even the 100% active substance alone, e.g. about 20-100% byweight of the active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. arthropods, i.e. insectsand a'carids, and more particularly, methods of combating at least oneof insects and acarids which comprise applying -to-at least one'ofcorrespondingly (a) such insects, (b) such-acarids, and (c) thecorresponding habitat,.i.'e. the locus to be protected, acorrespondingly.combative or toxic amount, iz'e; an arthropodicidally,especially insecticidally oracaricifdally, effective amount of theparticular active compound of the invention alone or together with acarrier vehicle as noted above. The instant formulations or compositionsare applied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, pouring,fumigating, and the like. 7

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend-upon the intended application. Therefore, in special cases'it is"possibleto go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention is illustrated without limitationby the following exarhples:

EXAMPLE ,1

Phaedon larvae test Solvent: 3 parts by weight acetone. Emulsifier: 1part by weight alkylaryl polyglycol ether To produce a suitablepreparation of the particular active compound, 1 part by weight of suchactive compound is mixed with the stated amount of solyent containnigthe stated amount of emulsifier; and the "resulting concentrate isdiluted with water to the desired final con; centration. y

Cabbage leaves (Brassica. oleracealare sprayed with this preparation ofthe given'active compound until dripping wet and then infested withmustard beetle larvae (Phaedon cochleariae).

After the period of time stated inthe following -table, the degree ofdestruction of thepests is determined and expressed as a percentage: 100means that all, and 0 means that none, of the beetle larvae are killed.v

The particular active compounds tested, their concentrations, theevaluation time and the experimental results obtained can be seen fromthe following Table 1:

TABLE 1 [Phaedon-larvae test] committa Degree of tion of activedestruction compound in in percent Active compound percent after 3 days(A) I? 0L1 wunmw-s-omQ (Known) (11) v 0.1 '10'0 -O\(") 0. 100 0.0/PS--OH2-CHu- 02115 2,) 0,1

7 C1-- O\(|II) 0. 01 i 100 0.00]; 80

, 1 -s on2-crn- (31%", or 'o 1 mo The instantO-alkyl-O-aryl-thiophosphoric acid esters are obtained in most cases inthe form of colorless to slightly colored water-insoluble oils, some ofwhich can be distilled under greatly reduced pressure withoutdecomposition. When this is not possible, the instant compounds can,however, by so-called slight distillation, that is brief heating tomoderately elevated temperatures in a vacuum, be freed from the lastvolatile components and so be purified.

As already mentioned, the compounds according to the present inventionare distinguished by an outstanding insecticidal and acaricidaleffectiveness and some of them also possess a good fungitoxic activity.The instant compounds have a low toxicity towards warm blooded animalsand a concomitantly low phytotoxicity. The pesticidal effect sets inrapidly and is long-lasting. By reason of these properties, the instantcompounds can be used for plant protection and the protection of storedproducts and in the hygiene field for the control of noxious sucking andeating insects and of mites and phytopathogenic fungi.

The main sucking insects contemplated herein include: aphids (Aphidae)such as the green peach aphid (Myrus perszcae), the bean aphid (Doralisfabae), the bird cherry aphid (Rhopalosiphum padi.), the pea aphid(Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), thecurrent gall aphid (Cryptomyzus korschelti), the mealy apple aphid(Sappaphis mall), the mealy plum aphid (Hyalopterus arundinis) and thecherry black-fly (Myzus cerasi); in addition, scales and mealybugs(Coccina), for example the Oleander scale (Aspidiotus hea erae) and thesoft scale (Lecanium hesperidum) as well as the grape mealybug(Pseudococcus maritimus); thrips (Thysanoptera), such as Hercinozhripsfemoralis, and bugs, for example the beet bug (Piesma quadrata), thecotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), theassassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans) andalso cicadas, such as Euscelz's bilobatus and Nepholettix biplmctatus;and the like.

In the case of the biting insects contemplated herein, above all theremay be mentioned: butterfly caterpillars (Lepidoptera) such as thediamond-back moth (Plutella maculipennis), the gipsy moth (Lymc'ntriadispar), the browntail moth (Euproctz's chrysorrhoea) and tentcaterpillar (Malascosoma neustria); further, the cabbage moth (Mamestraharmless) and the cutworm (Agroris segetum), the large white butterfly(Pieris brassicae), the small winter moth (Cheimatobia brumata), thegreen oak tortrix moth (Tortrz'x viridana), the fall armyworm (Laphygmafrugiperda) and cotton Worm (Prodenia litura), the crmine moth(Hyponomeuta padella), the Mediterranean flour moth (Ephestiakt'ihniella) and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein arebeetles (Coleoptera) for example the granary weevil (Sitophilusgranm'ius-Calandra granarza), the Colorado beetle (Leptz'notarsadecemlineata), the dock beetle (Gastrophysa viridula), the mustardbeetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus),the raspberry beetle (Byturus tomentosus), the bean weevil(BruchidiusAcantlzoscelides obtectus), the leather beetle (Dermestesfrischi), khapra beetle (Trogoderma granorium), the flour beetle(Tribolium castaneum), the northern corn billbug (Calandra or Sitophiluszeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm(Tenebrio molitor) and the saw-toothed grain beetle (Oryzaephilussurinamensis) and also species living in the soil, for example wireworms(Agritotes spec.) and larvae of the cockchafer (Melolontha melolontha);cockroaches, such as the German cockroach (Blattella germanica),American cockroach (Periplaneta americana), Madeira cockroach(Laucophaea or Rhyparobia madeirae), Oriental cockroach (Blattaorientalis), the giant cockroach (Blaberus giganteus) and the blackgiant cockroach (Blaberus fuscus) as well as Henschoutedeniaflexivz'tta; further, Orthoptera, for example the house cricket (Achetadomestica); termites such as the eastern subterranean termite(Reticulitermes flavipes) and Hymenoptera such as ants, for example thegarden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such asthe vinegar fly (Drosophila melan0- gaster), the Mediterranean fruit fly(Ceratitis capitata), the house fly (Musca domestica), the little housefly (Fannia canicularis), the blackbow fly (Phormia aegina) andblue-bottle fly (Calliphora erythorcephala) as well as the stable fly(Stomoxys calcitrans); further, gnats, for example mosquitoes such asthe yellow fever mosquito (Aedes aegypti), the northern house mosquito(Culex pipiens) and the malaria mosquito (Anopheles stephensi); and thelike.

With the mites (Acari) contemplated herein there are classed, inparticular, the spider mites (Tetranychidae) such as the two-spottedspider mite (Tetranychus telarius- Tetranychus althaeae or T etranychusurticae) and the European red mite (Paratetranychus pilosus-Panonychusulmi), blister mites, for example the currant blister mite (Eriophyesribis) and tarsonemids, for example the broad mite (Hemz'larsonemuslaws) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, suchas the relapsing fever tick (Ornithodorus moubata); and the like.

When used against hygiene pests and pests of stored products,particularly flies and mosquitoes, the instant compounds are alsodistinguished by an outstanding residual activity on Wood and clay and agood stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert pesticidal diluents or extenders, i.e. conventionalpesticidal dispersible carrier vehicles such as solutions, emulsions,suspensions, emulsifiable concentrates, spray powders, pastes, solublepowders, dusting agents, granules, etc. These are prepared in knownmanner, for instance by extending the active compounds with conventionalpesticidal dispersible liquid diluent carriers and/or dispersible solidcarriers optionally with the use of carrier vehicle assistants, e.g.conventional pesticidal surface-active agents, including emulsifyingagents and/or dispersing agents, whereby, for example, in the case wherewater is used as diluent, organic solvents may be added as auxiliarysolvents. The following may be chiefly considered for use asconventional carrier vehicles for this purpose: inert dispersible liquiddiluent carriers, including inert organic solvents, such as aromatichydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated,espectially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes,etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatichydrocarbons (e.g. methylene chloride, etc.) alcohols (e.g. methanol,ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.),ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides(e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide,etc.), ketones (e.g. acetone, etc.) and/or water; as well as inertdispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate,talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highlydispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereasthe following may be chiefly considered for use as conventional carriervehicle assistants, e.g surface-active agents, for this purpose:emulsifying agents, such as non-ionic and/or anionic emulsifying agents(e.g. polyethylene oxide esters of fatty acids, polyethylene oxideethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., andespecially alkyl arylpolyglycol ethers, magnesium stearate, sodiumoleate, etc.); and/or dispersing agents, such as lignin, sulfite Wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such Disclaimer 3,641,22L-Gerhard Sohmder,Vuppertal-Cronenberg, Ingeborg Hammamz, Cologne, and Wilhelm StemZeZ,Wuppertal-Vohwinkel, Germany. O-ALKYL-O-ARYL-THIOLPHOSPHORIC ACIDESTERS. Patent dated Feb. 8, 1972. Disclaimer filed May 26, 1976, by theassignee, Bay e7 Alctz'engesellschaft. Hereby enters this disclaimer toclaims 1, 3 and 4 of said patent.

[Oflicz'al Gazette August 10, 1 976.]

